Pesticidally active thiophene derivatives

ABSTRACT

Compounds of formula (I), as defined herein, to processes for preparing them, to pesticidal, in particular insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control pests such as insect, acarine, molluse and nematode pests.

The present invention relates to pyrazole derivatives, to processes forpreparing them, to intermediates for preparing them, to pesticidal, inparticular insecticidal, acaricidal, molluscicidal and nematicidalcompositions comprising those derivatives and to methods of using themto combat and control pests such as insect, acarine, mollusc andnematode pests.

It has now surprisingly been found that certain pyrazole derivativeshave highly potent insecticidal properties. Other compounds in this areaare known from WO2014/122083, WO2012/107434, WO2015/067646,WO2015/067647, WO2015/067648, WO2015/150442, WO2015/193218 andWO2010/051926.

Thus, as embodiment 1, the present invention provides a compound offormula (I),

wherein

Y¹ and Y³ are independently selected from H, halogen, cyano,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylsulfanyl, C₁-C₆-haloalkylsulfanyl,C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl andC₁-C₆-haloalkylsulfonyl;

Y⁵ is -i-CF(CF₃)(CF₃) or -1-CF₃-cyclopropyl;

A is CH or N;

R¹ is selected from H, C₁-C₆-alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₇cycloalkyl, C₃-C₇ cycloalkyl-C₁-C₃-alkyl, —C(═O)H, C₁-C₆-alkylcarbonyl,C₃-C₇-cycloalkylcarbonyl, C₁-C₆-alkoxycarbonyl, aryl(C₀-C₃)-alkyl andheteroaryl(C₀-C₃)-alkyl, wherein each of C₁-C₆-alkyl, C₃-C₆ alkenyl,C₃-C₆ alkynyl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkyl-C₁-C₃-alkyl,C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxycarbonyl, aryl(C₀-C₃)-alkyl andheteroaryl(C₀-C₃)-alkyl is unsubstituted or substituted with 1 to 5substituents independently selected from halogen, cyano, C₁-C₆-alkoxyand C₁-C₆-alkoxycarbonyl;

R² is selected from halogen, cyano, C₁-C₆-alkyl and C₁-C₆-haloalkyl;

Q is H or cyano;

or an agrochemically acceptable salt or N-oxide thereof.

As embodiment 2, there is provided the compound according to embodiment1 wherein R² is selected from halogen and cyano.

As embodiment 3, there is provided the compound according to embodiment1 or 2 wherein R² is selected from chloro and cyano.

As embodiment 4, there is provided the compound according to any one ofembodiment 1 to 3 wherein R² is cyano.

As embodiment 5, there is provided the compound according to any one ofembodiment 1 to 4 wherein Q is cyano.

As embodiment 5.1, there is provided the compound according to any oneof embodiment 1 to 4 wherein Q is H.

As embodiment 6, there is provided the compound according to any one ofembodiments 1 to 5 wherein R¹ is selected from H, methyl, ethyl,—C(═O)H, —CH₂CH═CH₂, isobutyl, isopropyl, 2,2,2-trifluoroethyl,—C(═O)CH₃, —C(═O)CH₂CH₃, —C(═O)cyclopropyl, —C(═O)OCH₃, —C(═O)OCH₂CH₃,—C(═O)CH(CH₃)(CH₃), —CH₂C≡CH, —CH₂CN, —CH₂—O—CH₃, —CH₂—O—CH₂—CH₃ and—CH₂-cyclopropyl.

As embodiment 7, there is provided the compound according to any one ofembodiments 1 to 6 wherein R¹ is selected from H, isobutyl,2,2,2-trifluoroethyl, —C(═O)CH₃, —C(═O)OCH₃, —C(═O)OCH₂CH₃,—C(═O)CH(CH₃)(CH₃), —CH₂—C—CH, —CH₂CN, —CH₂—O—CH₃ and —CH₂-cyclopropyl.

As embodiment 8, there is provided the compound according to any one ofembodiments 1 to 7 wherein Y¹ and Y³ are independently selected from H,chloro, bromo, —CF₃, —CHF₂, —OCF₃, —OCHF₂, methyl, ethyl, —SCH₃, —SOCH₃,—S(O)₂CH₃ and CN.

As embodiment 8.1, there is provided the compound according to any oneof embodiments 1 to 7 wherein Y¹ and Y³ are independently selected fromchloro, bromo, —CF₃, —CHF₂, —OCF₃, —OCHF₂, methyl, ethyl, —SCH₃, —SOCH₃,—S(O)₂CH₃ and CN.

As embodiment 9, there is provided the compound according to any one ofembodiments 1 to 8 wherein Y¹ and Y³ are independently selected fromchloro, bromo, —CF₃, —OCHF₂ and methyl.

As embodiment 10, there is provided the compound according to embodiment1 of formula (I)

wherein

Y¹ and Y³ are independently selected from chloro, bromo, —CF₃, —OCHF₂and methyl;

Y⁵ is -i-CF(CF₃)(CF₃) or -1-CF₃-cyclopropyl;

A is CH;

R¹ is selected from H, methyl, ethyl, isobutyl, 2,2,2-trifluoroethyl,—C(═O)CH₃, —C(═O)OCH₃, —C(═O)OCH₂CH₃, —C(═O)CH(CH₃)(CH₃), —CH₂—C—CH,—CH₂CN, —CH₂—O—CH₃ and —CH₂-cyclopropyl;

R² is cyano;

Q is H or cyano;

or an agrochemically acceptable salt or N-oxide thereof.

As embodiment 11, there is provided the compound according to embodiment1 of formula (I)

wherein

Y¹ and Y³ are independently selected from chloro, bromo, —CF₃, —OCHF₂and methyl;

Y⁵ is -i-CF(CF₃)(CF₃) or -1-CF₃-cyclopropyl;

A is N;

R¹ is selected from H, methyl, ethyl, isobutyl, 2,2,2-trifluoroethyl,—C(═O)CH₃, —C(═O)OCH₃, —C(═O)OCH₂CH₃, —C(═O)CH(CH₃)(CH₃), —CH₂—C—CH,—CH₂CN, —CH₂—O—CH₃ and —CH₂-cyclopropyl;

R² is cyano;

Q is H or cyano;

or an agrochemically acceptable salt or N-oxide thereof.

As embodiment 11.1, there is provided the compound according toembodiment 10 or 11 wherein Y⁵ is -i-CF(CF₃)(CF₃).

As embodiment 12: A compound or salt according to embodiment 1 selectedfrom

Ex. No. Structure Name 1

2-cyano-N-cyclopropyl-5-[1-[2,6- dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]thiophene-3-carboxamide 2

2-chloro-N-cyclopropyl-5-[1-[2,6- dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]thiophene-3-carboxamide 3

2-cyano-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]thiophene-3-carboxamide 4

2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]thiophene-3-carboxamide 5

2-cyano-N-cyclopropyl-5-[1-[2,6- dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]thiophene-3-carboxamide 6

2-chloro-5-[1-[2-chloro-4-[1,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]-N-(1-cyanocyclopropyl)thiophene-3- carboxamide 7

5-[1-[2-bromo-6-chloro-4-[1,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]-2-chloro-N-(1-cyanocyclopropyl)thiophene-3- carboxamide 8

5-[1-[2-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]-2-cyano-N-cyclopropyl-thiophene-3-carboxamide 9

5-[1-[2-bromo-6-chloro-4-[1,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]-2-chloro-N-cyclopropyl-thiophene-3-carboxamide 10

2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol- 4-yl]thiophene-3-carboxamide 11

2-cyano-N-cyclopropyl-5-[1-[2,6- dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]-N-ethyl-thiophene-3-carboxamide 12

2-cyano-N-cyclopropyl-5-[1-[2,6- dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4- yl]-N-methyl-thiophene-3-carboxamide 13

2-cyano-N-cyclopropyl-5-[1-[2,6- dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4- yl]thiophene-3-carboxamide 14

2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]-N-ethyl-thiophene-3-carboxamide 15

2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4- yl]-N-methyl-thiophene-3-carboxamide 16

2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4- yl]thiophene-3-carboxamide 17

2-chloro-N-cyclopropyl-5-[1-[2,6- dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4- yl]thiophene-3-carboxamide

Definitions:

The term “alkyl” as used herein—in isolation or as part of a chemicalgroup—represents straight-chain or branched hydrocarbons, preferablywith 1 bis 6 carbon atoms, for example methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl,1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl and2-ethylbutyl. Alkyl groups with 1 to 4 carbon atoms are preferred, forexample methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butylor t-butyl.

The term “alkenyl”—in isolation or as part of a chemicalgroup—represents straight-chain or branched hydrocarbons, preferablywith 2 bis 6 carbon atoms and at least one double bond, for examplevinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl,2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1, 1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl. Alkenylgroups with 2 to 4 carbon atoms are preferred, for example 2-propenyl,2-butenyl or 1-methyl-2-propenyl.

The term “alkynyl”—in isolation or as part of a chemicalgroup—represents straight-chain or branched hydrocarbons, preferablywith 2 bis 6 carbon atoms and at least one triple bond, for example2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and2,5-hexadiynyl. Alkynyls with 2 to 4 carbon atoms are preferred, forexample ethynyl, 2-propynyl or 2-butynyl-2-propenyl.

The term “cycloalkyl”—in isolation or as part of a chemicalgroup—represents saturated or partially unsaturated mono-, bi- ortricyclic hydrocarbons, preferably 3 to 10 carbon atoms, for examplecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl.

Cycloalkyls with 3, 4, 5, 6 or 7 carbon atoms are preferred, for examplecyclopropyl or cyclobutyl.

The term “heterocycloalkyl”—in isolation or as part of a chemicalgroup—represents saturated or partially unsaturated mono-, bi- ortricyclic hydrocarbons, preferably 3 to 10 carbon atoms, for examplecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl,wherein one or more of the ring atoms, preferably 1 to 4, morepreferably 1, 2 or 3 of the ring atoms are independently selected fromN, 0, S, P, B, Si and Se, more preferably N, O and S, wherein no O atomscan be located next to each other.

The term “alkylcycloalkyl” represents mono-, bi-oder tricyclicalkylcycloalkyl, preferably with 4 to 10 or 4 to 7 carbon atoms, forexample ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and4-methyl-cyclohexyl. Alkylcycloalkyls with 4, 5 or 7 carbon atoms arepreferred, for example ethylcyclopropyl or 4-methyl-cyclohexyl.

The term “cycloalkylalkyl” represents mono, bi- or tricycliccycloalkylalkyls, preferably 4 to 10 or 4 to 7 carbon atoms, for examplecyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyland cyclopentylethyl. Cycloalkylalkyls with 4, 5 or 7 carbon atoms arepreferred, for example cyclopropylmethyl or cyclobutylmethyl.

The term “halogen” or “halo” represents fluoro, chloro, bromo or iodo,particularly fluoro, chloro or bromo. The chemical groups which aresubstituted with halogen, for example haloalkyl, halocycloalkyl,haloalkyloxy, haloalkylsulfanyl, haloalkylsulfinyl or haloalkylsulfonylare substituted one or up to the maximum number of substituents withhalogen. If “alkyl”, “alkenyl” or “alkynyl” are substituted withhalogen, the halogen atoms can be the same or different and can be boundat the same carbon atom or different carbon atoms.

The term “halocycloalkyl” represents mono-, bi- or tricyclichalocycloalkyl, preferably with 3 to 10 carbon atoms, for example1-fluoro-cyclopropyl, 2-fluoro-cyclopropyl or 1-fluoro-cyclobutyl.Preferred halocycloalkyl with 3, 5 or 7 carbon atoms.

The term “haloalkyl”, “haloalkenyl” or “haloalkynyl” represents alkyls,alkenyls or alkynyls substituted with halogen, preferably with 1 to 9halogen atoms that are the same or different, for example monohaloalkyls(=monohaloalkyl) like CH₂CH₂Cl, CH₂CH₂F, CHClCH₃, CHFCH₃, CH₂Cl, CH₂F;perhaloalkyls like CCl₃ or CF₃ or CF₂CF₃; polyhaloalkyls like CHF₂,CH₂F, CH₂CHFCl, CF₂CF₂H, CH₂CF₃. The same applies for haloalkenyl andother groups substituted by halogen. Examples of haloalkoxy are forexample OCF₃, OCHF₂, OCH₂F, OCF₂CF₃, OCH₂CF₃, OCF₃, OCHF₂, OCH₂F,OCF₂CF₃, OCH₂CF₃.

Further examples of haloalkyls are trichloromethyl,chlorodifluoromethyl, dichlorofluoromethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, pentafluoroethyl andpentafluoro-t-butyl.

Haloalkyls having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5 ofthe same or different halogen atoms selected from fluoro, chloro orbromo, are preferred.

Haloalkyls having 1 or 2 carbon atoms and 1 to 5 gleichen of the same ordifferent halogen atoms selected from fluoro or chloro, for exampledifluoromethyl, trifluoromethyl or 2,2-difluoroethyl, are particularlypreferred.

The term “hydroxyalkyl” represents straight or branched chain alcohols,preferably with 1 to 6 carbon atoms, for example methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, s-butanol and t-butanol.Hydroxyalkyls having 1 to 4 carbon atoms are preferred.

The term “alkoxy” represents straight or branched chain 0-alkyl,preferably having 1 to 6 carbon atoms, for example methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy and t-butoxy.Alkoxy having 1 to 4 carbon atoms are preferred.

The term “haloalkoxy” represents straight or branched chain 0-alkylsubstituted with halogen, preferably with 1 to 6 carbon atoms, forexample difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2,2,2-Trifluoroethoxy and2-Chloro-1,1,2-trifluoroethoxy.

Haloalkoxy having 1 to 4 carbon atoms are preferred.

The term “alkylsulfanyl” represents straight or branched chain S-alkyl,preferably with 1 to 6 carbon atoms, for example methylthio, ethylthio,n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio andt-butylthio. Alkylsulfanyl having 1 to 4 carbon atoms are preferred.Examples for haloalkylsulfanyl, i.e. with halogen substitutedalkylsulfanyl, are for example difluoromethylthio, trifluoromethylthio,trichloromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio,2-fluoroethylthio, 2,2-difluoroethylthio, 1,1,2,2-tetrafluoroethylthio,2,2,2-trifluoroethylthio or 2-chloro-1,1,2-trifluoroethylthio.

The term “alkylsulfinyl” represents straight or branched chainalkylsulfinyl (—S(O)alkyl), preferably having 1 to 6 carbon atoms, forexample methylsulfinyl, ethylsulfinyl, n-propylsulfinyl,isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, s-butylsulfinyland t-butylsulfinyl.

Alkylsulfinyls having 1 to 4 carbon atoms are preferred. Examples ofhaloalkylsulfinyls, i.e. with halogen substituted alkylsulfinyls, aredifluoromethylsulfinyl, trifluoromethylsulfinyl,trichloromethylsulfinyl, chlorodifluoromethylsulfinyl,1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl,1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and2-chloro-1,1,2-trifluoroethylsulfinyl.

The term “alkylsulfonyl” represents straight or branched chainalkylsulfonyl (—S(O)₂alkyl), preferably having 1 to 6 carbon atoms, forexample methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, s-butylsulfonyland t-butylsulfonyl. Alkylsulfonyls having 1 to 4 carbon atoms arepreferred.

Examples of haloalkylsulfonyls, i.e. with halogen substitutedalkylsulfonyls, are for example difluoromethylsulfonyl,trifluoromethylsulfonyl, trichloromethylsulfonyl,chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl,2-fluoroethylsulfonyl, 2,2-difluoroethylsulfonyl,1,1,2,2-tetrafluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and2-chloro-1,1,2-trifluoroethylsulfonyl.

The term “alkylcarbonyl” represents straight or branched chainalkyl-C(═O), preferably having 2 to 7 carbon atoms, for examplemethylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl,s-butylcarbonyl and t-butylcarbonyl.

Alkylcarbonyls having 1 to 4 carbon atoms are preferred.

The term “cycloalkylcarbonyl” represents cycloalkyl-carbonyl, preferably3 to 10 carbon atoms in the cycloalkyl part, for examplecyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl,cyclohexyl-carbonyl, cycloheptyl-carbonyl, cyclooctylcarbonyl,bicyclo[2.2.1]heptyl, bycyclo[2.2.2]octylcarbonyl and adamantylcarbonyl.Cycloalkylcarbonyls having 3, 5 or 7 carbon atoms in the cycloalkyl partare preferred.

The term “alkoxycarbonyl”—in isolation or as part of a chemicalgroup—represents straight or branched chain alkoxycarbonyl, preferablyhaving 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkoxy part,for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,isopropoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl.

The term “alkylaminocarbonyl” represents straight or branched chainalkylaminocarbonyl having preferably 1 to 6 carbon atoms or 1 to 4carbon atoms in the alkyl part, for example methylaminocarbonyl,ethylaminocarbonyl, n-proylaminocarbonyl, isopropyl-aminocarbonyl,s-butylaminocarbonyl and t-butylaminocarbonyl.

The term “N,N-Dialkylamino-carbonyl” “represents straight or branchedchain N,N-dialkylaminocarbonyl with preferably 1 to 6 carbon atoms or 1to 4 carbon atoms in the alkyl part, for exampleN,N-Dimethylamino-carbonyl, N,N-diethylamino-carbonyl,N,N-di(n-propylamino)-carbonyl, N,N-di-(isopropylamino)-carbonyl andN,N-di-(s-butylamino)-carbonyl.

The term “aryl” represents a mono-, bi- or polycyclical aromatic systemwith preferably 6 to 14, more preferably 6 to 10 ring-carbon atoms, forexample phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl.“Aryl” also represents polycyclic systems, for exampletetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl. Arylalkylsare examples of substituted aryls, which may be further substituted withthe same or different substituents both at the aryl or alkyl part.Benzyl and 1-phenylethyl are examples of such arylalkyls.

The term “heteroaryl” represents heteroaromatic groups, i.e. completelyunsaturated aromatic heterocyclic groups, which fall under the abovedefinition of heterocycles. “Heteroaryls” with 5 to 7-membered ringswith 1 to 3, preferably 1 or 2 of the same or different heteroatomsselected from N, O, and S. Examples of “heteroaryls” are furyl, thienyl,pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl,thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl,azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl and1,2,4-diazepinyl.

A compound according to any one of embodiments 1 to 12 which has atleast one basic centre can form, for example, acid addition salts, forexample with strong inorganic acids such as mineral acids, for exampleperchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorusacid or a hydrohalic acid, with strong organic carboxylic acids, such asC₁-C₄alkanecarboxylic acids which are unsubstituted or substituted, forexample by halogen, for example acetic acid, such as saturated orunsaturated dicarboxylic acids, for example oxalic acid, malonic acid,succinic acid, maleic acid, fumaric acid or phthalic acid, such ashydroxycarboxylic acids, for example ascorbic acid, lactic acid, malicacid, tartaric acid or citric acid, or such as benzoic acid, or withorganic sulfonic acids, such as C₁-C₄alkane- or arylsulfonic acids whichare unsubstituted or substituted, for example by halogen, for examplemethane- or p-toluenesulfonic acid. A compounds according to any one ofembodiments 1 to 12 which have at least one acidic group can form, forexample, salts with bases, for example mineral salts such as alkalimetal or alkaline earth metal salts, for example sodium, potassium ormagnesium salts, or salts with ammonia or an organic amine, such asmorpholine, piperidine, pyrrolidine, a mono-, di- ortri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine.

Compounds according to any one of embodiments 1 to 12 also includehydrates which may be formed during the salt formation.

As used herein, when one embodiment refers to several other embodimentsby using the term “according to any one of”, for example “according toany one of embodiments 1 to 5”, then said embodiment refers not only toembodiments indicated by the integers such as 1 and 2 but also toembodiments indicated by numbers with a decimal component such as 1.1,1.2 or 2.1, 2.2, 2.3. For example, “according to any one of embodiments1 to 3” means for example according to any one of embodiments 1, 1.1, 2,3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7.

The compounds according to any one of embodiments 1 to 12 may be made bya variety of methods well known to a person skilled in the art or asshown in Schemes 1 to 5. Further instructions regarding the preparationcan be found in WO2015/067646, WO2015/150442, WO2015/193218,WO2014/122083, WO2012/107434 and WO2011/113756.

The compounds according to any one of embodiments may be made by avariety of methods known to a person skilled in the art or as shown inSchemes 1 to 5.

For example, compounds of formula (I) can be prepared according toScheme 1.

wherein Y¹, Y³, Y⁵, A, R¹, Q and R² are as defined in any one ofembodiments 1 to 12.

1) Compounds of formula (I) may be prepared by reacting a compound offormula (II) wherein P is OH, C₁-C₆alkoxy or Cl, F or Br, with an amineof formula (IV), as shown in Scheme 1. When P is OH such reactions areusually carried out in the presence of a suitable coupling reagent, suchas N,N′-dicyclohexylcarbodiimide (“DCC”),1-ethyl-3-(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”) orbis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-CI”), in the presenceof a base, and optionally in the presence of a nucleophilic catalyst,such as hydroxybenzotriazole (“HOBT”). When P is CI, such reactions areusually carried out in the presence of a base, and optionally in thepresence of a nucleophilic catalyst. Alternatively, it is possible toconduct the reaction in a biphasic system comprising an organic solvent,preferably ethyl acetate, and an aqueous solvent, preferably a solutionof sodium hydrogen carbonate. When P is C₁-C₆alkoxy it is sometimespossible to convert the ester directly to the amide by heating the esterand amine together in a thermal process. Suitable bases includepyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) ordiisopropylethylamine (Hunig's base). Preferred solvents areN,N-dimethylacetamide, tetrahydrofuran, dioxane, 1,2-dimethoxyethane,ethyl acetate and toluene. The reaction is carried out at a temperatureof from 0° C. to 100° C., preferably from 15° C. to 30° C., inparticular at ambient temperature.

2) Acid halides of formula (II), wherein P is Cl, F or Br, may be madefrom carboxylic acids of formula (II), wherein P is OH, under standardconditions, known from a person skilled in the art.

3) Carboxylic acids of formula (II), wherein P is OH, may be formed fromesters of formula (II), wherein P is C₁-C₆alkoxy under standardconditions, known from a person skilled in the art.

4) Compounds of formula (I) may be prepared by reacting a compound offormula (III) wherein X is a leaving group, for example a halogen, suchas bromo, with carbon monoxide and an amine of formula (IV), in thepresence of a catalyst, such as palladium(II) acetate orbis(triphenylphosphine)palladium(II) dichloride, optionally in thepresence of a ligand, such as triphenylphosphine, and a base, such assodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine(“DMAP”) or diisopropyl-ethylamine (Hunig's base), in a solvent, such aswater, N,N-dimethylformamide or tetrahydrofuran. The reaction is carriedout at a temperature of from 50° C. to 200° C., preferably from 100° C.to 150° C. The reaction is carried out at a pressure of from 50 to 200bar, preferably from 100 to 150 bar.

6) Compounds of formula (II), wherein P is OH, may be prepared byreacting a compound of formula (III) wherein X is a leaving group, forexample a triflate or a halogen, such as bromo, with carbon monoxide orpotassium formate, in the presence of a catalyst, such as palladium(II)acetate or bis-(triphenylphosphine)palladium(II) dichloride, optionallyin the presence of a ligand, such as triphenylphosphine,diphenylphosphinoferrocene (“dppf”) and a base, such as sodiumcarbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”)or diisopropylethylamine (Hunig's base), in a solvent, such as water,N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran. Thereaction is carried out at a temperature of from 50° C. to 200° C.,preferably from 100° C. to 150° C. The reaction is carried out at apressure of CO from 50 to 200 bar, preferably from 100 to 150 bar.

7) Compounds of formula (II), wherein P is C₁-C₆alkoxy, may be preparedby reacting a compound of formula (III) wherein X is a leaving group,for example a triflate or a halogen, such as bromo, with carbon monoxideand an alcohol, in the presence of a catalyst, such as palladium(II)acetate or bis-(triphenylphosphine)palladium(II) dichloride, optionallyin the presence of a ligand, such as triphenylphosphine, and a base,such as sodium carbonate, pyridine, triethylamine,4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig'sbase), in a solvent, such as water, N,N-dimethylformamide,methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out ata temperature of from 50° C. to 200° C., preferably from 100° C. to 150°C. The reaction is carried out at a pressure of carbon monoxide from 50to 200 bar, preferably from 100 to 150 bar.

8) Alternatively, compounds of formula (II), wherein P is OH, may beprepared by reacting a compound of formula (III) wherein X is a halogen,such as bromo, with magnesium or butyllithium, in order to prepare theintermediate Grignard reagent or respectively the organolithium reagent,followed by its reaction with carbon dioxide, in a solvent, such asdiethyl ether, diisopropyl ether, tert-butyl methyl ether,methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out ata temperature of from −80° C. to 60° C., preferably from −20° C. to 40°C. The preparation of the intermediate Grignard reagent (halogen-metalreactions) can also be performed using isopropylmagnesium chloride, inthe presence or absence of alkali salts, such as lithium chloride.

wherein Y¹, Y³, Y⁵, A and R² are as defined in any one of embodiments 1to 12.

9) Compounds of formula (II), wherein P is OH or C₁-C₆alkoxy, may beprepared by reacting a compound of formula (V) wherein U represents aboronic acid, boronic ester or trifluoroboronate or —SnBu₃ or —ZnCl witha compound of formula (VII), wherein X^(B) represents bromine, chlorine,iodine or triflate, using known processes from the literature usingpalladium-catalyzed reactions. For instance, the reactions can becarried out in the presence of a catalyst, such as palladium(II)acetate, palladium(0) tetrakis-triphenylphosphine orbis(triphenylphosphine)palladium(II) dichloride, optionally in thepresence of a ligand, such as triphenylphosphine,diphenylphosphinoferrocene (“dppf”) and a base, such as sodiumcarbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”)or diisopropylethylamine (Hunig's base), in a solvent, such as water,N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran. Thereaction is carried out at a temperature of from 50° C. to 200° C.,preferably from 100° C. to 150° C. The compounds of the generalstructure (VII) are either commercially available or may be prepared byprocesses known from to the person skilled in the art.

10) Compounds of formula (III) wherein X is a leaving group, for examplea triflate or a halogen, such as bromo, may be prepared by reacting acompound of formula (V) wherein U represents a boronic acid, boronicester or trifluoroboronate or —SnBu₃ or —ZnCl with a compound of formula(VI), wherein X^(B) represents bromo, chloro, iodo or triflate, usingknown processes from the literature using palladium-catalyzed reactions.For instance, the reactions can be carried out in the presence of acatalyst, such as palladium(II) acetate, palladium(O)tetrakis-triphenylphosphine or bis(triphenylphosphine)palladium(II)dichloride, optionally in the presence of a ligand, such astriphenylphosphine, diphenylphosphinoferrocene (“dppf”) and a base, suchas sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine(“DMAP”) or diisopropylethylamine (Hunig's base), in a solvent, such aswater, N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran.The reaction is carried out at a temperature of from 50° C. to 200° C.,preferably from 100° C. to 150° C. The compounds of the generalstructure (VI) are either commercially available or may be prepared byprocesses known from to the person skilled in the art. The compounds ofthe general structure (V) may be prepared as described in the literature(WO2015067647).

wherein Y¹, Y³, Y⁵, A, R¹, Q and R² are as defined in any one ofembodiments 1 to 12.

11) Compounds of formula (I), may be prepared by reacting a compound offormula (V) wherein U represents a boronic acid, boronic ester ortrifluoroboronate or —SnBu₃ or —ZnCl with a compound of formula (VIII),wherein X^(B) represents bromo, chloro, iodo or triflate, using knownprocesses from the literature using palladium-catalyzed reactions. Thecompounds of the general structure (VIII) may be prepared by processesknown from to the person skilled in the art.

wherein Y¹, Y³, Y⁵, A, R¹, Q and R² are as defined in any one ofembodiments 1 to 12.

12) Compounds of formula (I), may be prepared by reacting a compound offormula (IX) wherein X is a halogen, with a compound of formula (X),using known processes from the literature, either by nucleophilicsubstitution at the aromatic ring (X═Cl or F), or by a transitionmetal-catalyzed reaction (X═Br or I), for instance, using a palladium orcopper-catalyzed reactions. The compounds of the general structure (IX)and (Xa) may be prepared by processes known from to the person skilledin the art.

wherein Y¹, Y³, Y⁵, R¹, Q and R² are as defined in any one ofembodiments 1 to 12.

13) Compounds of formula (Ia), may be prepared by reacting a compound offormula (XII) with a compound of formula (XI), using known processesfrom the literature, optionally in the presence of copper or a coppercatalyst, such as copper sulfate or copper (I) iodide, and optionally inthe presence of a base, such as N-ethyldiisopropylamine, in the presenceof a solvent or a mixture of solvents, such as t-butanol, water. In thecase of a Cu(II) catalyst, a reducing agent, such as sodium ascorbatemay be used. In the case of a Cu(0) catalyst, such as an amine salt, anoxidising agent may be used. (See, for example: Angewandte Chemie,International Edition (2009), 48(27), 4900-4908 and cited references,Angew. Chem. Int. Ed. 2008, 47, 2182-2184 and cited references, and Eur.J. Org. Chem. 2006, 51-68 and cited references. The compounds of thegeneral structure (XI) and (XII) may be prepared by processes known fromto the person skilled in the art, or as is described in WO2011/113756.

A compound according to any one of embodiments 1 to 12 can be convertedin a manner known per se into another compound according to any one ofembodiments 1 to 12 by replacing one or more substituents of thestarting compound according to any one of embodiments 1 to 12 in thecustomary manner by (an)other substituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula (I) can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds according to anyone of embodiments 1 to 12 are obtained by treatment with a suitableacid or a suitable ion exchanger reagent and salts with bases areobtained by treatment with a suitable base or with a suitable ionexchanger reagent.

Salts of compounds according to any one of embodiments 1 to 12 can beconverted in the customary manner into the free compounds, acid additionsalts, for example, by treatment with a suitable basic compound or witha suitable ion exchanger reagent and salts with bases, for example, bytreatment with a suitable acid or with a suitable ion exchanger reagent.

Salts of compounds according to any one of embodiments 1 to 12 can beconverted in a manner known per se into other salts of compoundsaccording to any one of embodiments 1 to 12, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compoundsaccording to any one of embodiments 1 to 12, which have salt-formingproperties can be obtained in free form or in the form of salts.

The compounds according to any one of embodiments 1 to 12 and, whereappropriate, the tautomers thereof, in each case in free form or in saltform, can be present in the form of one of the stereoisomers which arepossible or as a mixture of these, for example in the form of purestereoisomers, such as antipodes and/or diastereomers, or asstereoisomer mixtures, such as enantiomer mixtures, for exampleracemates, diastereomer mixtures or racemate mixtures, depending on thenumber, absolute and relative configuration of asymmetric carbon atomswhich occur in the molecule and/or depending on the configuration ofnon-aromatic double bonds which occur in the molecule; the inventionrelates to the pure stereoisomers and also to all stereoisomer mixtureswhich are possible and is to be understood in each case in this sensehereinabove and hereinbelow, even when stereochemical details are notmentioned specifically in each case.

Diastereomer mixtures or racemate mixtures of compounds according to anyone of embodiments 1 to 12, in free form or in salt form, which can beobtained depending on which starting materials and procedures have beenchosen can be separated in a known manner into the pure diasteromers orracemates on the basis of the physicochemical differences of thecomponents, for example by fractional crystallization, distillationand/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable stereoisomer mixtures, butalso by generally known methods of diastereoselective orenantioselective synthesis, for example by carrying out the processaccording to the invention with starting materials of a suitablestereochemistry.

N-oxides can be prepared by reacting a compound according to any one ofembodiments 1 to 12 with a suitable oxidizing agent, for example theH₂O₂/urea adduct in the presence of an acid anhydride, e.g.trifluoroacetic anhydride. Such oxidations are known from theliterature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO00/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective stereoisomer, for example enantiomer ordiastereomer, or stereoisomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds according to any one of embodiments 1 to 12 and, whereappropriate, the tautomers thereof, in each case in free form or in saltform, can, if appropriate, also be obtained in the form of hydratesand/or include other solvents, for example those which may have beenused for the crystallization of compounds which are present in solidform.

The following Examples illustrate, but do not limit, the invention.

The compounds of the invention can be distinguished from known compoundsby virtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, δ ppm, 3 ppm, 1.5 ppm or 0.8ppm.

The present invention also provides intermediates useful for thepreparation of compounds according to any one of embodiments 1 to 12.Certain intermediates are novel and as such form a further aspect of theinvention.

One group of novel intermediates are compounds of formula (II)

wherein Y¹, Y³, Y⁵, A and R² are as defined in any one of embodiments 1to 12, and P is hydroxy, C₁-C₁₅-alkoxy or halogen, such as bromo, chloroor fluoro. The preferences for Y¹, Y³, Y⁵, A and R² are the same as thepreferences set out for the corresponding substituents of a compoundaccording to any one of embodiments 1 to 12.

Another group of novel intermediates are compounds of formula (Ill)

wherein Y¹, Y³, Y⁵, A and R² are as defined in any one of embodiments 1to 12, and X is a halogen, amino, hydroxyl, C₁-C₈alkoxy, cyano,C₁-C₈alkylsulfonyloxy, C₁-C₈haloalkylsulfonyloxy, C₁-C₈arylsulfonyloxy,optionally substituted C₁-C₈arylsulfonyloxy (aryl is preferably phenyl),diazonium salts (e.g. X is —N₂ ⁺Cl⁻, —N₂ ⁺BF₄ ⁻, —N₂ ⁺Br⁻, —N₂ ⁺PF₆ ⁻),phosphonate esters (e.g. —OP(O)(OR′)₂, wherein R′ is methyl or ethyl),preferably bromo, iodo, chloro, cyano, trifluoromethylsulfoxy,p-toluenesulfoxy, diazonium chloride. The preferences for Y¹, Y³, Y⁵, Aand R² are the same as the preferences set out for the correspondingsubstituents of a compound according to any one of embodiments 1 to 12.

One group of novel intermediates are compounds of formula (XI)

wherein R¹, R² and Q are as defined in any one of embodiments 1 to 12.The preferences for R¹, R² and Q are the same as the preferences set outfor the corresponding substituents of a compound according to any one ofembodiments 1 to 12.

One group of novel intermediates are compounds of formula (X)

wherein R¹, R², A and Q are as defined in any one of embodiments 1 to12. The preferences for R¹, R², A and Q are the same as the preferencesset out for the corresponding substituents of a compound according toany one of embodiments 1 to 12.

One group of novel intermediates are compounds of formula (VIII)

wherein R¹, R² and Q are as defined in any one of embodiments 1 to 12and X is a halogen, amino, cyano, C₁-C₈alkylsulfonyloxy,C₁-C₈haloalkylsulfonyloxy, C₁-C₈arylsulfonyloxy, optionally substitutedC₁-C₈arylsulfonyloxy (aryl is preferably phenyl), diazonium salts (e.g.X is —N₂ ⁺Cl⁻, —N₂ ⁺BF₄ ⁻, —N₂ ⁺Br, —N₂ ⁺PF₆ ⁻), phosphonate esters(e.g. —OP(O)(OR′)₂, wherein R′ is methyl or ethyl), preferably bromo,iodo, chloro, cyano, trifluoromethylsulfoxy, p-toluenesulfoxy anddiazonium chloride. The preferences for R¹, R² and Q are the same as thepreferences set out for the corresponding substituents of a compoundaccording to any one of embodiments 1 to 12.

The compounds according to any one of embodiments 1 to 12 arepreventively and/or curatively valuable active ingredients in the fieldof pest control, even at low rates of application, which have a veryfavorable biocidal spectrum and are well tolerated by warm-bloodedspecies, fish and plants. The active ingredients according to theinvention act against all or individual developmental stages of normallysensitive, but also resistant, animal pests, such as insects orrepresentatives of the order Acarina. The insecticidal or acaricidalactivity of the active ingredients according to the invention canmanifest itself directly, i. e. in destruction of the pests, which takesplace either immediately or only after some time has elapsed, forexample during ecdysis, or indirectly, for example in a reducedoviposition and/or hatching rate.

Examples of the above mentioned animal pests are:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsadecem Lineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.;

from the order Diptera, for example,

Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Hemiptera, for example,

Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens; Acyrthosium pisum, Adalgesspp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp,Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus,Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiellaspp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani,Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicorynebrassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp.,Chrysomphalus conidium, Chrysomphalus dictyospermi, Cicadella spp,Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum,Dalbulus maidis, Dialeurodes spp, Diaphorina citri, Diuraphis noxia,Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae,Hyalopterus spp, Hyperomyzus pallidus, Idioscopus clypealis, Jacobiascalybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphiserysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfapruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.,Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piriMats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae,Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinusmaidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcusspp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelisseriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp.,Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera,Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp,Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae,Unaspis citri, Zygina flammigera, Zyginidia scutellaris;

from the order Hymenoptera, for example,

Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplo-campa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminate

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Gra-pholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatoes) and Chilo supressalis (preferablyin rice).

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds according to any one of embodiments 1 to 12 may also haveactivity against the molluscs. Examples of which include, for example,Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A.rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C.Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve,D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G.trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigonaarbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L.flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M.gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata);Vallonia and Zanitoides.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab,are known. In the case of modified toxins, one or more amino acids ofthe naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278,WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Crops may also be modified for enhanced resistance to fungal (forexample Fusarium, Anthracnose, or Phytophthora), bacterial (for examplePseudomonas) or viral (for example potato leafroll virus, tomato spottedwilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes,such as the soybean cyst nematode.

Crops that are tolerant to abiotic stress include those that haveenhanced tolerance to drought, high salt, high temperature, chill,frost, or light radiation, for example through expression of NF-YB orother proteins known in the art.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO95/33818) orprotein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store rooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In another embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072,WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp.,Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharine.

In one aspect, the invention therefore also relates to pesticidalcompositions such as emulsifiable concentrates, suspension concentrates,microemulsions, oil dispersibles, directly sprayable or dilutablesolutions, spreadable pastes, dilute emulsions, soluble powders,dispersible powders, wettable powders, dusts, granules or encapsulationsin polymeric substances, which comprise—at least—one of the activeingredients according to any one of embodiments 1 to 12 and which are tobe selected to suit the intended aims and the prevailing circumstances.In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable adsorptive carriers for granulesare porous types, such as pumice, brick grit, sepiolite or bentonite,and suitable non-sorptive carrier materials are calcite or sand. Inaddition, a large number of granulated materials of inorganic or organicnature can be used, in particular dolomite or communited plant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having1 to approximately 10 carbon atoms in the alkyl chain and approximately20 to approximately 250 ethylene glycol ether groups and approximately10 to approximately 100 propylene glycol ether groups. Normally, theabovementioned compounds contain 1 to approximately 5 ethylene glycolunits per propylene glycol unit. Examples which may be mentioned arenonylphenoxypolyethoxyethanol, castor oil polyglycol ether,polypropylene glycol/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethylammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps orwater-soluble synthetic surface-active compounds. Examples of suitablesoaps are the alkali, alkaline earth or (unsubstituted or substituted)ammonium salts of fatty acids having approximately 10 to approximately22 C atoms, such as the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which are obtainable for examplefrom coconut or tall oil; mention must also be made of the fatty acidmethyl taurates. However, synthetic surfactants are used morefrequently, in particular fatty sulfonates, fatty sulfates, sulfonatedbenzimidazole derivatives or alkylaryl sulfonates. As a rule, the fattysulfonates and fatty sulfates are present as alkali, alkaline earth or(substituted or unsubstituted) ammonium salts and they generally have analkyl radical of approximately 8 to approximately 22 C atoms, alkyl alsoto be understood as including the alkyl moiety of acyl radicals;examples which may be mentioned are the sodium or calcium salts oflignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcoholsulfate mixture prepared from natural fatty acids. This group alsoincludes the salts of the sulfuric esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonyl groups and a fatty acid radical ofapproximately 8 to approximately 22 C atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolammonium saltsof decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid/formaldehyde condensate. Also possible are,furthermore, suitable phosphates, such as salts of the phosphoric esterof a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids. As arule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, ofactive ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least onesolid or liquid adjuvant, it being possible as a rule for 0 to 25%,especially 0.1 to 20%, of the composition to be surfactants(% in eachcase meaning percent by weight). Whereas concentrated compositions tendto be preferred for commercial goods, the end consumer as a rule usesdilute compositions which have substantially lower concentrations ofactive ingredient.

Typically, a pre-mix formulation for foliar application comprises 0.1 to99.9%, especially 1 to 95%, of the desired ingredients, and 99.9 to0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, forexample, a solvent such as water), where the auxiliaries can be asurfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on thepre-mix formulation.

Normally, a tank-mix formulation for seed treatment applicationcomprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients,and 99.75 to 20%, especially 99 to 25%, of a solid or liquid auxiliaries(including, for example, a solvent such as water), where the auxiliariescan be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%,based on the tank-mix formulation.

Typically, a pre-mix formulation for seed treatment applicationcomprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients,and 99.5 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant(including, for example, a solvent such as water), where the auxiliariescan be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%,based on the pre-mix formulation.

Whereas commercial products will preferably be formulated asconcentrates (e.g., pre-mix composition (formulation)), the end userwill normally employ dilute formulations (e.g., tank mix composition).

Preferred seed treatment pre-mix formulations are aqueous suspensionconcentrates. The formulation can be applied to the seeds usingconventional treating techniques and machines, such as fluidized bedtechniques, the roller mill method, rotostatic seed treaters, and drumcoaters. Other methods, such as spouted beds may also be useful. Theseeds may be presized before coating. After coating, the seeds aretypically dried and then transferred to a sizing machine for sizing.Such procedures are known in the art.

In general, the pre-mix compositions of the invention contain 0.5 to99.9 especially 1 to 95, advantageously 1 to 50%, by mass of the desiredingredients, and 99.5 to 0.1, especially 99 to 5%, by mass of a solid orliquid adjuvant (including, for example, a solvent such as water), wherethe auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to50, especially 0.5 to 40%, by mass based on the mass of the pre-mixformulation.

Examples of foliar formulation types for pre-mix compositions are:

GR: Granules

WP: wettable powders

WG: water dispersable granules (powders)

SG: water soluble granules

SL: soluble concentrates

EC: emulsifiable concentrate

EW: emulsions, oil in water

ME: micro-emulsion

SC: aqueous suspension concentrate

CS: aqueous capsule suspension

OD: oil-based suspension concentrate, and

SE: aqueous suspo-emulsion.

Whereas, examples of seed treatment formulation types for pre-mixcompositions are:

WS: wettable powders for seed treatment slurry

LS: solution for seed treatment

ES: emulsions for seed treatment

FS: suspension concentrate for seed treatment

WG: water dispersible granules, and

CS: aqueous capsule suspension.

Examples of formulation types suitable for tank-mix compositions aresolutions, dilute emulsions, suspensions, or a mixture thereof, anddusts.

Preferred compositions are composed in particular as follows (%=percentby weight):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 5 to 20%

surfactant: 1 to 30%, preferably 10 to 20%

solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surfactant: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surfactant: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 99%, preferably 15 to 98%

Granulates:

active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

EXAMPLES

The following compounds according to embodiment 1 may be preparedaccording to the methods described herein or according to known methods.

Experimental

The following examples are intended to illustrate the invention and arenot to be construed as being limitations thereon.

“Mp” means melting point in ° C. ¹H NMR measurements were recorded on aBrucker 400 MHz spectrometer, chemical shifts are given in ppm relevantto a TMS standard. Spectra measured in deuterated solvents as indicated.

LC MS Method A: Standard:

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

LC MS Method B: Standard Long:

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

LC MS Method C: Unpolar:

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min40% B, 60% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Example 1: Preparation of2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamidea) Preparation of 1 ethyl 5-bromo-2-cyano-thiophene-3-carboxylate

To a solution of ethyl 2,5-dibromothiophene-3-carboxylate (4 g) in 12 mLDMF were added copper cyanide (1.23 g) and Pd(PPh₃)₄ (291 mg) and thereaction mixture was heated to 80° C. for 21 h. The reaction mixture waspoured onto 200 mL of a stirred mixture of ethyl acetate/cyclohexane(3:1), the solids were filtered off through a pad of celite and thefiltrate was washed three times with a saturated aqueous solution ofsodium carbonate then once with brine. The organic phase was dried oversodium sulfate, filtered and concentrated under reduced pressure. Thecrude product was purified by flash chromatography (silica,cyclohexane/ethyl acetate) to afford the title product as a white solid.

¹H NMR (400 MHz, CDCl₃) δ ppm 1.45 (t, 3H), 4.55 (q, 3H), 7.58 (s, 1H).

LC-MS (Method A): t_(R)=0.99 min, m/z=260 [M+1], 262 [M+3].

b) Preparation of 5-bromo-2-cyano-thiophene-3-carboxylic acid

A solution of ethyl 5-bromo-2-cyano-thiophene-3-carboxylate (0.250 g) intetrahydrofurane (3.44 ml) and water (0.96 ml) was treated with lithiumhydroxide (0.101 g) and was stirred at 20° C. for 2 hours. The reactionmixture was acidified with conc. Aqueous hydrochloric acid and themixture was extracted with ethyl acetate. The organic layer was washedwith water, then with brine and dried over sodium sulfate. Evaporationof the solvent yielded the title compound as a yellow powder that wasused without purification for the following step.

¹H-NMR (d6-DMSO, 400 MHz, δ in ppm): 7.71 (s, 1H).

c) Preparation of 5-bromo-2-cyano-N-cyclopropyl-thiophene-3-carboxamide

A solution of 5-bromo-2-cyano-thiophene-3-carboxylic acid (0.228 g) indichloromethane (4.55 ml) was treated with oxalyl chloride (0.231 g) anda catalytic amount of N,N-dimethylformamide. After 0.5 hour, thereaction mixture was concentrated under reduced pressure and the residuewas dissolved in tetrahydrofurane (4.5 ml). This solution was slowlyadded to a solution of cyclopropylamine (0.106 g) in tetrahydrofurane(4.5 ml) under stirring. After 15 hours, the reaction mixture wastreated with an aqueous solution of sodium hydrogen carbonate andextracted twice with dichloromethane. The organic phase was dried oversodium sulfate. The crude product was purified by chromatography oversilica gel, eluting with a mixture of ethyl acetate-cyclohexane (3:7).Evaporation of the selected fractions left the title compound as a paleyellow solid.

¹H-NMR (CDCl_(3, 400) MHz, δ in ppm): 7.48 (s, 1H), 6.50 (br. s, 1H),2.91 (m, 1H), 0.95-0.87 (m, 2H), 0.72-0.67 (m, 2H).

d) Preparation of[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]hydrazine

To a suspension of2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline)(3.3 g) in 15 mL solution of HCl (6N) at 0-5° C. was added dropwise asolution of NaNO₂ (897 mg) in 10 mL water then the solution was stirredfor 20 min at 0-5° C. then it was added dropwise at room temperature tothe solution of SnCl₂ (5.68 g) in 25 mL aqueous HCl (6N). Theprecipitate was filtered and washed with water. The resulting wet cakewas suspended in water and the pH was adjusted to 10 and the organicmaterial was extracted into ethyl acetate, the organic phase was driedover sodium sulfate, filtered and evaporated. The crude product waspurified by flash chromatography (silica, DCM) to afford the titleproduct as a white solid.

¹H NMR (300 MHz, CDCl₃) δ ppm: 4.0-4.1 (brs, 2H), 5.78-5.9 (brs, 1H),7.47 (s, 2H).

e) Preparation of1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole

To the a solution of[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]hydrazine(424 mg) in EtOH (1.43 mL) were added tetramethoxypropane (202 mg) andH₂SO₄ (62 mg) and the reaction mixture was heated to 80° C. for 3 h. Thereaction mixture was partitioned between ethyl acetate and a saturatedsolution of NaHCO₃, the layers were separated, the aqueous phase wasextracted with ethyl acetate and the combined organic phase was driedover magnesium sulfate, filtered and concentrated under reducedpressure. The residue was purified by flash chromatography (silica,cyclohexane/gradient of ethyl acetate) to afford the title compound.

¹H NMR (300 MHz, CDCl₃) δ ppm: 6.55 (t, 1H), 7.61 (m, 1H), 7.71 (s, 2H),7.85 (m, 1H).

f) Preparation of1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-iodo-pyrazole

To a solution of1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole(1.81 g) in 25 mL acetonitrile was added dropwise a solution ofN-iodosuccinimide (5.36 g) in 35 mL acetonitrile over 10 min and thereaction mixture was heated to reflux for 5 h. The reaction mixture wasconcentrated under reduced pressure then poured onto of a mixture ofethyl acetate/water, the aqueous phase was separated and extracted twicewith ethyl acetate. The combined organic phases were washed with asaturated solution of sodium carbonate then brine and dried over sodiumsulfate, filtered and concentrated under reduced pressure. The crudeproduct was purified by flash chromatography (silica, cyclohexane/ethylacetate) to afford the title product as a beige solid.

¹H NMR (300 MHz, CDCl₃) δ ppm 7.64 (s, 1H), 7.71 (m, 2H), 7.83 (s, 1H).mp° C. 92-96° C.

g) Preparation of1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole

In a microwave tube,1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-iodo-pyrazole(2.23 g),4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane(1.11 g) and potassium acetate (1.09 g) were dissolved in 11 mldimethylsulfoxide. The mixture was purged with argon for 5 min.[1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (66 mg) wasadded and the mixture was heated to 80° C. for 4 h. The reaction mixturewas diluted with ethyl acetate, filtered through a pad of celite, thefiltrate was washed with a saturated solution of ammonium chloride andbrine. The organic phase was dried over sodium sulfate, filtered andevaporated. The resulting brown oil was progressed to the next stepwithout purification.

LC-MS (Method A): t_(R)=1.32 min, m/z=508 [M+1].

h) Preparation of ethyl2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylate

In a flask,1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole(467 mg), 1 ethyl 5-bromo-2-cyano-thiophene-3-carboxylate (200 mg) weredissolved in 5.4 mL of DMF. The mixture was purged with argon for 5 minthen Pd(PPh₃)₄ (89 mg) and a solution of potassium carbonate (322 g) in0.76 mL of water were added and the mixture was heated at 85° C. for 3h. The reaction mixture was diluted with ethyl acetate, filtered througha pad of celite, the filtrate was washed with water and brine. Theorganic phase was dried over sodium sulfate, filtered and concentratedunder reduced pressure. The crude brown oil was purified by flashchromatography (silica, ethyl acetate/cyclohexane) to afford the tiltecompound as an oil.

¹H NMR (400 MHz, CDCl₃) δ ppm 1H NMR (400 MHz, CDCl3) δ ppm 1.45 (t,3H), 4.45 (q, 2H), 7.62 (s, 1H), 7.78 (s, 2H), 7.9 (s, 1H), 8.1 (s, 1H).

LC-MS (Method A): t_(R)=1.30 min, m/z=560 [M+1].

i) Preparation of2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylicacid

A mixture of ethyl2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-pyrazol-4-yl]thiophene-3-carboxylate(220 mg), lithium hydroxide (28 mg), tetrahydrofuran (3.1 mL) and water(0.4 mL) was stirred at room temperature for 3 h. The mixture wasacidified with 1 N HCl and the product was extracted with ethyl acetate.The extract was dried over sodium sulfate, filtered and evaporated toafford a white solid.

LC-MS (Method A): t_(R)=1.15 min, m/z=532 [M+1].

j) Preparation of2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide

To a stirred solution of2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-pyrazol-4-yl]thiophene-3-carboxylicacid (265 mg) in DMF (2 mL) were added HATU (228 mg), cyclopropylamine(33 mg), N,N.diisopropylethylamine (177 mg) and the reaction mixture wasstirred at room temperature overnight. The reaction mixture waspartitioned between ethyl acetate and a saturated solution of ammoniumchloride, the layers were separated and the organic phase was washedwith brine, dried over magnesium sulfate, filtered and concentratedunder reduced pressure. The residue was purified by flash chromatography(silica, cyclohexane/gradient of ethyl acetate) to afford a white solid.

¹H NMR (400 MHz, CDCl₃) δ ppm 1H NMR (400 MHz, CDCl3) δ ppm: 0.69-0.73(m, 2H), 0.90-0.98 (m, 2H), 2.9-3.0 (m, 1H), 6.6 (brs, 1H), 7.58 (s,1H), 7.78 (s, 2H), 7.90 (s, 1H), 8.08 (s, 1H). ¹⁹F NMR (376 MHz, CDCl₃)δ ppm −182 (m, 1F), −75 (m, 6F).

LC-MS (Method A): t_(R)=1.18 min, m/z=571 [M+1].

Example 2: Preparation of2-chloro-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamidea) Preparation of2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylicacid

In a flask,1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole(892 mg), 5-bromo-2-chloro-thiophene-3-carboxylic acid (200 mg) weredissolved in 4.9 mL of DMF. The mixture was purged with argon for 5 min.Pd(PPh₃)₄ (96 mg) and a solution of potassium carbonate (347 mg) in 1.0mL of water were added and the mixture was heated at 80° C. for 3 h. Themixture was diluted with ethyl acetate and poured onto a solution of HCl0.5 M, the mixture was extracted with ethyl acetate. The combinedorganic layers were dried over sodium sulfate, filtered and evaporated.The crude was redissolved in DCM and extracted with an aqueous solutionof NaOH (0.5 M), the combined basic water phase was acidified to pH=2with an aqueous solution of HCl (6N) and extracted with ethyl acetatethree times. The combined organic phases were dried over sodium sulfate,filtrated and evaporated to give the title product as a beige solid.

LC-MS (Method A): t_(R)=1.21 min, m/z=539 [M−1], 541 [M+1].

b) Preparation of2-chloro-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide

To a stirred solution of2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)-ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylicacid (175 mg) in DMF (1.2 mL) were added HATU (164 mg), cyclopropylamine(24 mg), N,N.diisopropylethylamine (127 mg) and the reaction mixture wasstirred at room temperature for 2 h. The reaction mixture waspartitioned between ethyl acetate and a saturated solution of ammoniumchloride, the layers were separated and the organic phase was washedwith brine, dried over magnesium sulfate, filtered and concentratedunder reduced pressure. The residue was purified by flash chromatography(silica, cyclohexane/gradient of ethyl acetate) to afford the titlecompound as a white solid.

1H NMR (400 MHz, CDCl3) δ ppm: 0.60-0.70 (m, 2H), 0.85-0.95 (m, 2H),3.88-3.98 (m, 1H), 6.63 (brs, 1H), 7.48 (s, 1H), 7.75 (s, 2H), 7.77 (s,1H), 7.98 (s, 1H).

¹⁹F NMR (376 MHz, CDCl₃) δ ppm −181.6 (m, 1F), −74.5 (m, 6F).

LC-MS (Method A): t_(R)=1.18 min, m/z=571 [M+1].

Example 16: Preparation of2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamidea) Preparation of2-azido-1,3-dichloro-5-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]benzene

To a stirred solution of con.HCl (80 mL) and H₂O (40 mL),2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline(5.00 g) was added followed by NaNO₂ (1.00 g) at 0° C. The reactionmixture was stirred for 10 min, ^(t)BuOH (40 mL) and NaN₃ (1.5 g) wereadded and the whole was stirred for 18 h. The aqueous layer wasextracted twice with ethyl acetate (200 ml).The combined organic phaseswere dried over sodium sulfate and concentrated. The residue waspurified by column chromatography (PE: EA=10:1) to afford the titlecompound (4 g) ¹H NMR (400 MHz, cdcl₃) δ 7.53 (s, 2H).

b) Preparation of ethyl2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylate

To a stirred solution of THF (20 mL) and H₂O (10 mL),2-azido-1,3-dichloro-5-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]benzene(1.78 g) and ethyl 2-chloro-5-ethynyl-thiophene-3-carboxylate (1.07 g),CuSO₄.5H₂O (100 mg), L-ascorbic acid sodium salt (198 mg) were added atroom temperature. The mixture was stirred for 18 h at room temperature.The crude mixture was diluted with ethyl acetate and washed with waterand brine, dried over magnesium sulfate and evaporated. The residue waspurified by column chromatography on silica gel (PE/EA=4:1) to givetitle compound (1.54 g) ¹H NMR (400 MHz, CDCl₃) δ 7.92 (s, 1H), 7.79 (s,2H), 7.67 (s, 1H), 4.37 (d, J=7.1 Hz, 2H), 1.40 (t, J=6.9 Hz, 3H).

c) Preparation of2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylicacid

To a solution of ethyl2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylate(1.54 g) in EtOH (10 ml) was added NaOH (220 mg) and water (1 ml). Themixture was stirred for 2 h at room temperature and then acidified with1 N HCl. The mixture was extracted with dichloromethane. The extract wasdried over magnesium sulfate and evaporated to afford title compound asa yellow solid.

d) Preparation of example 16:2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide

To a solution of2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylicacid (100 mg) in 3 ml of DMF was added 1-aminocyclopropanecarbonitrilehydrochloride (50 mg), HATU (110 mg) and DIPEA (100 mg) and the reactionmixture was stirred at room temperature overnight and then poured intowater (50 mL). The aqueous solution was then extracted 3 times withethyl acetate (150 mL), the combined organic phases were washed twicewith brine (200 mL) before being dried on magnesium sulfate, filteredand concentrated. The residue was purified by flash chromatography onsilica gel using PE/EA(4:1) as eluent to afford title compound (65 mg).

¹H NMR (400 MHz, DMSO-d6) δ 9.32 (s, 1H), 9.04(s, 1H), 8.18 (s, 2H),7.71(s, 1H), 1.56(s, 2H),1.26(s, 2H).

¹⁹F NMR (283 MHz, CDCl₃) δ −82.60(d, 6F, J=7.2 Hz), −188.46 (s, 1F).

Example 14: Preparation of2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide

To a solution of2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide(60.0 mg) and Cs₂CO₃ (80 mg) in DMF (0.5 mL) was added iodoethane (60mg) at room temperature. The mixture was stirred at 50° C. for 1 h, andthen diluted with ethyl acetate. The organic layer was washed with waterand brine, dried over Na₂SO₄ and concentrated. The residue was furtherpurified by column chromatography eluting with PE:EA=2:1 to give titleproduct (30 mg).

¹H NMR (400 MHz, DMSO-d⁶) δ9.04(s, 1H), 8.18 (s, 2H),7.62 (s, 1H), 3.42(s, 2H) 1.65(s, 3H),1.43(s, 2H),1.21(s, 2H).

¹⁹F NMR (283 MHz, CDCl₃) δ −82.55(d, 6F, J=7.2 Hz), −188.39(s, 1F).

Preparation of Intermediates:

Preparation of2-cyano-N-cyclopropyl-5-(2-trimethylsilylethynyl)thiophene-3-carboxamide

To a solution of 5-bromo-2-cyano-N-cyclopropyl-thiophene-3-carboxamide(1.49 g) in tetrahydrofurane (38.5 ml), under inert atmosphere, wasadded N,N-diisopropylethylamine (0.952 g), then cuprous iodide (0.053g), bis-triphenylphosphine palladium dichloride (0.197 g) andtrimethylsilylacetylene (0.826 g).The reaction mixture was stirred for18 hours at 20° C., at which time, LC-MS analysis showed that thestarting material was consumed. The reaction mixture was diluted withethyl acetate and washed three times with water, then with brine anddried over sodium sulfate. The crude product was purified bychromatography over silica gel, eluting with a mixture of ethylacetate-cyclohexane. Evaporation of the selected fractions delivered thetitle compound.

¹H-NMR (CDCl₃, 400 MHz, δ in ppm): 7.50 (s, 1H), 6.46 (br. s, 1H), 2.91(m, 1H), 0.94-0.87 (m, 2H), 0.71-0.65 (m, 2H), 0.28 (s, 9H).

Preparation of 2-cyano-N-cyclopropyl-5-ethynyl-thiophene-3-carboxamide

A solution of2-cyano-N-cyclopropyl-5-(2-trimethylsilylethynyl)thiophene-3-carboxamide(described above) (1.36 g) in tetrahydrofurane (47 ml), cooled at 0° C.,under inert atmosphere, was treated dropwise with a solution oftetrabutylammonium fluoride (1 M in tetrahydrofurane) (9.48 ml). After20 minutes, LC-MS analysis showed the consumption of the startingmaterial. The reaction was poured into water and the resulting mixturewas extracted three times with ethyl acetate. The combined organiclayers were washed with brine and dried over sodium sulfate. Afterremoval of the solvent under reduced pressure, the crude product wassubmitted to chromatography over silica gel, eluting with a mixture ofethyl acetate and cyclohexane. Evaporation of the selected fractionsdelivered the title compound.

¹H-NMR (CDCl₃, 400 MHz, δ in ppm): 7.58 (s, 1H), 6.51 (br. s, 1H), 3.57(s, 1H), 2.92 (m, 1H), 0.96-0.85 (m, 2H), 0.75-0.62 (m, 2H).

Preparation of methyl 2-chloro-5-iodo-thiophene-3-carboxylate

To a solution of 1.7 g of methyl 2-chlorothiophene-3-carboxylate and 0.1g of HClO₄ in 20 mL of CH₃CN was added 2.3 g of NIS. The reaction wasstirred at room temperature for 6 h then stirred at 50° C. for 24 h.Then the reaction mixture was poured into water and extracted with ethylacetate three times. The combined organic layers were dried over sodiumsulfate, filtered and concentrated under vacuum to give 2.2 g of thetitle compound.

¹HNMR (400 MHz, d₆-DMSO): δ (ppm) 7.55 (s, 1H), 3.77 (s, 3H).

Preparation of methyl2-chloro-5-(2-trimethylsilylethynyl)thiophene-3-carboxylate

To a 5 mL dry solution of Et₃N solution was successively added 1.2 g ofmethyl 2-chloro-5-iodo-thiophene-3-carboxylate, 400 mg ofethynyl(trimethyl)silane, 28 mg of PdCl₂(PPh₃)₂ 38 mg of CuI under a N₂atmosphere. The mixture was heated at 70° C. for 2 h. After cooling themixture to room temperature, EtOAc was added and the suspension wasfiltered through a Celite pad. The filtrate was collected and evaporatedunder reduced pressure. The residue was purified by columnchromatography on silica gel (petroleum ether/ethyl acetate=2:1) to give1.2 g of title compound.

¹HNMR (400 MHz, CDCl₃): δ (ppm) 7.43 (s, 1H), 3.87 (s, 3H), 0.25 (s,9H).

methyl 2-chloro-5-ethynyl-thiophene-3-carboxylate

To a solution of 1.3 g of methyl2-chloro-5-(2-trimethylsilylethynyl)thiophene-3-carboxylate in 50 mL ofTHF (50 mL), 10 mL of tetrabutylammonium fluoride (1M solution in THF)was added dropwise at room temperature. The reaction mixture was stirredat room temperature for 0.5 h. Then the reaction mixture was poured intowater and extracted with ethyl acetate three times. The combined organiclayers were dried over sodium sulfate, filtered and concentrated undervacuum to give 0.8 g of title product which was used without furtherpurification.

Preparation of 2,5-dibromo-N-cyclopropyl-thiophene-3-carboxamide

A solution of 5-bromo-2-cyano-thiophene-3-carboxylic acid (2.0 g) indichloromethane (34.97 ml) was treated with oxalyl chloride (1.77 g) anda catalytic amount of N,N-dimethylformamide at room temperature. After1.5 hour, the reaction mixture was concentrated under reduced pressureand the residue was dissolved in tetrahydrofuran (35 mL). This solutionwas slowly added to a solution of cyclopropylamine (815 mg) intetrahydrofuran (35 mL) under stirring. After 1 hour, the reactionmixture was treated with an aqueous solution of sodium bicarbonate andextracted twice with dichloromethane. The organic phase was dried oversodium sulfate. The crude product was purified by chromatography oversilica gel, eluting with a mixture of ethyl acetate-cyclohexane (2:8).Evaporation of the selected fractions left the title compound as a whitepowder.

¹H-NMR (CDCl₃, 400 MHz, δ in ppm): 0.58-0.68 (m, 2H), 0.80-0.92 (m, 2H),2.82-2.91 (m, 1H), 6.5 (brs, 1H), 7.32 (s, 1H).

Preparation of 5-bromo-2-cyano-N-cyclopropyl-thiophene-3-carboxamide

A solution of 5-bromo-2-cyano-thiophene-3-carboxylic acid (221 mg g) indichloromethane (7.62 ml) was added 1-amino-1-cyclopropanecarbonitrilehydrochloride (124 mg), triethylamine (292 mg), HOAT (146 mg) and EDChydrochloride (205 mg) and the reaction mixture was stirred at roomtemperature for 17 h. The reaction mixture was concentrated under vacuumand the residue was purified by chromatography over silica gel, elutingwith a mixture of ethyl acetate-cyclohexane. Evaporation of the selectedfractions left the title compound as a yellow solid.

¹H-NMR (DMSO, 400 MHz, δ in ppm): 1.28-1.32 (m, 2H), 1.58-1.62 (m, 2H),7.8 (s, 1H), 9.5 (s, 1H).

The following compounds which have been characterized were prepared inanalogy to Example 1, 2, 14 and 16.

TABLE 1 Examples of compounds of formula (I): Ex. Structure ¹H-NMR (400MHz) ¹⁹F NMR 3

(CDCl₃) δ ppm: 1.42- 1.48 (m, 2H), 1.70-1.75 (m, 2H), 6.94 (brs, 1H),7.63 (s, 1H), 7.78 (s, 2H), 7.91 (s, 1H), 8.08 (s, 1H) (377 MHz, CDCl₃)δ ppm −181.5 (m, 1F), −75.18 (m, 6F) 4

(CDCl₃) δ ppm: 1.38- 1.43 (m, 2H), 1.58-1.62 (m, 2H), 7.02 (brs, 1H),7.50 (s, 1H), 7.76 (s, 2H), 7.79 (s, 1H), 7.99 (s, 1H) (377 MHz, CDCl₃)δ ppm −181.6 (m, 1F), −75.2 (m, 6F) 5

(CDCl3) δ ppm 8.05- 7.99 (m, 1 H) 7.83-7.78 (m, 1 H) 7.59-7.53 (m, 1 H)7.47-7.40 (m, 2 H) 6.58-6.49 (m, 1 H) 3.01- 2.91 (m, 1 H) 2.16 (s, 6 H)0.99-0.89 (m, 2 H) 0.77-0.68 (m, 2 H) (377 MHz, CDCl3) δ ppm −75.43 (s,6 F) −181.92 (s, 1 F) 6

(CDCl3) δ ppm 8.22- 8.15 (m, 1 H) 7.96-7.90 (m, 1 H) 7.88-7.81 (m, 2 H)7.71-7.65 (m, 1 H) 7.53-7.46 (m, 1 H) 7.11- 7.01 (m, 1 H) 1.75- 1.66 (m,2 H) 1.44-1.36 (m, 2 H) (377 MHz, CDCl3) δ ppm −75.44 (s, 6 F) −182.02(s, 1 F) 7

(CDCl3) δ ppm 8.00- 7.97 (m, 1 H) 7.94-7.89 (m, 1 H) 7.82-7.76 (m, 2 H)7.52-7.48 (m, 1 H) 7.09-7.03 (m, 1 H) 1.73- 1.66 (m, 2 H) 1.44- 1.37 (m,2H) (377 MHz, CDCl3) δ ppm −75.18 (s, 6 F) −182.02(s, 1 F) 8

(CDCl3) δ ppm 8.31- 8.27 (m, 1 H) 8.02-7.99 (m, 1 H) 7.86-7.81 (m, 2 H)7.71-7.66 (m, 1 H) 7.59-7.56 (m, 1 H) 6.56- 6.49 (m, 1 H) 2.99- 2.89 (m,1 H) 0.97-0.90 (m, 2 H) 0.75-0.67 (m, 2 H) (377 MHz, CDCl3) δ ppm −75.43(s, 6 F) −181.86(s, 1 F) 9

(CDCl3) δ ppm 8.08- 8.05 (m, 1 H) 7.92-7.88 (m, 2 H) 7.81-7.77 (m, 1 H)7.60-7.56 (m, 1 H) 6.59-6.52 (m, 1 H) 2.98- 2.91 (m, 1 H) 0.97- 0.89 (m,2 H) 0.75-0.68 (m, 2 H) (377 MHz, CDCl3) δ ppm −75.18 (s, 6 F)−181.54(s, 1 F) 10

(CDCl3) δ ppm 7.95- 7.88 (m, 1 H) 7.71-7.65 (m, 1 H) 7.48-7.45 (m, 1 H)7.45-7.39 (m, 2 H) 7.10-7.03 (m, 1 H) 2.16 (s, 6 H) 1.73-1.67 (m, 2 H)1.44 1.36 (m, 2 H) (377 MHz, CDCl3) δ ppm −75.45 (s, 6 F) −181.22(s, 1F) 11

(DMSO-D6) δ ppm 9.24 (s, 1H), 8.22 (s, 2H), 7.92 (s, 1H), 3.53 (s, 2H),2.94 (s, 1H), 1.22 (s, 3H), 0.69 (s, 2H), 0.58 (s, 2H). (283 MHz, CDCl₃)δ ppm −82.80 (d, 6F, J = 7.2 Hz), −188.64 (s, 1F) 12

(DMSO-D6) δ ppm 9.23 (s, 1H), 8.21 (s, 2H), 7.94 (s, 1H), 3.03 (s, 3H),2.94 (s, 1H), 0.66 (s, 2H), 0.58 (s, 2H). (283 MHz, CDCl₃) δ ppm −82.80(d, 6F, J = 7.2 Hz), −188.61 (s, 1F). 13

(DMSO-D6) δ ppm 9.21 (s, 1H), 8.80 (s, 1H), 8.22 (s, 2H), 8.04 (s, 1H),2.87 (s, 1H), 0.75 (d, J = 6.7 Hz, 2H), 0.60 (s, 2H). (283 MHz, CDCl₃) δppm −82.61 (d, 6F, J = 7.2 Hz), −188.44 (s, 1F). 15

(DMSO-D6) δ ppm 9.03(s, 1H), 8.17 (s, 2H), 7.59 (s, 1H), 3.02 (s, 3H)1.42(s, 2H), 1.21(s, 2H). (283 MHz, CDCl₃) δ ppm −82.60(d, 6F, J = 7.2Hz), −188.45 (s, 1F). 17

(DMSO-D6) δ ppm 9.03 (s, 1H), 8.44(s, 1H), 8.18 (s, 2H), 7.63 (s, 1H),2.80 (s, 1H), 0.67- 0.69(d, J = 6.7 Hz, 2H), 0.53 (s, 2H) (283 MHz,CDCl₃) δ ppm −82.47(d, 6F, J = 7.2 Hz), −188.33 (s, 1F).

Formulation Examples (%=Percent by Weight) Example F1

Emulsion concentrates a) b) c) Active ingredient 25% 40% 50% Calciumdodecylbenzenesulfonate  5%  8%  6% Castor oil polyethylene  5% — —glycol ether (36 mol of EO) Tributylphenoxypolyethylene — 12%  4% glycolether (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

Example F2

Solutions a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycolmonomethyl 20% — — — ether Polyethylene glycol — 70% — — MW 400N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1%  5%Petroleum ether — — 94%  — (boiling range: 160-190°)

The solutions are suitable for use in the form of microdrops.

Example F3

Granules a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin 94%  — 79%54% Highly disperse silica 1% — 13%  7% Attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo.

Example F4

Dusts a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc97%  — Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient.

Example F5

Wettable powders a) b) c) Active ingredient 25%  50% 75% Sodiumlignosulfonate 5%  5% — Sodium lauryl sulfate 3% —  5% Sodiumdiisobutyl- —  6% 10% naphthalenesulfonate Octylphenoxypolyethylene — 2% — glycol ether (7-8 mol of EO) Highly disperse silica 5% 10% 10%Kaolin 62%  27% —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration.

Example F6

Extruder granules Active ingredient 10% Sodium lignosulfonate  2%Carboxymethylcellulose  1% Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air.

Example F7

Coated granules Active ingredient 3% Polyethylene glycol (MW 200) 3%Kaolin 94% 

In a mixer, the finely ground active ingredient is applied uniformly tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules.

Example F8

Suspension concentrate Active ingredient 40% Ethylene glycol 10%Nonylphenoxypolyethylene glycol ether (15 mol of EO)  6% Sodiumlignosulfonate 10% Carboxymethylcellulose  1% 37% aqueous formaldehydesolution 0.2%  Silicone oil (75% aqueous emulsion) 0.8%  Water 32%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

Example F9

Powders for dry seed treatment a) b) c) active ingredient 25% 50% 75%light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — — 20%

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Example F10

Emulsifiable concentrate active ingredient 10% octylphenol polyethyleneglycol ether  3% (4-5 mol of ethylene oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol ofethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Example F11

Flowable concentrate for seed treatment active ingredients 40% propylene glycol 5% copolymer butanol PO/EO 2% Tristyrenephenole with10-20 moles EO 2% 1,2-benzisothiazolin-3-one (in the form of a 20%solution in 0.5%  water) monoazo-pigment calcium salt 5% Silicone oil(in the form of a 75% emulsion in water) 0.2%  Water 45.3%  

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds according to any one ofembodiments 1 to 12 with other insecticidally, acaricidally and/orfungicidally active ingredients may also have further surprisingadvantages which can also be described, in a wider sense, as synergisticactivity. For example, better tolerance by plants, reducedphytotoxicity, insects can be controlled in their different developmentstages or better behaviour during their production, for example duringgrinding or mixing, during their storage or during their use.

Suitable additions to active ingredients here are, for example,representatives of the following classes of active ingredients:organophosphorus compounds, nitrophenol derivatives, thioureas, juvenilehormones, formamidines, benzophenone derivatives, ureas, pyrrolederivatives, carbamates, pyrethroids, chlorinated hydrocarbons,acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoidsand Bacillus thuringiensis preparations.

The following mixtures of the compounds according to any one ofembodiments 1 to 12 with active ingredients are preferred (theabbreviation “TX” means “one compound selected from the compoundsaccording to any one of embodiments 1 to 12, preferably one compoundfrom embodiment 12):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX, an acaricide selected fromthe group of substances consisting of1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternativename) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name)[CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate (alternative name)+TX, bromo-cyclen (918)+TX, bromophos(920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin(99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben(alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX,camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX,carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50′439 (developmentcode) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX,chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate(975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX,chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl(146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II(696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel(alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternativename) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate(1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin(196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT(219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O(1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternativename)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX,dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name)(653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton(269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX,dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX,dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPACname) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton(278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternativename) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX,eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX,permethrin (626)+TX, petroleum oils (alternative name) (628)+TX,phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX,phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes(traditional name) (1347)+TX, polynactins (alternative name) (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name)[CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen(738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep(753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX,tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam(alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox(alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX,thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternativename) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX, an algicideselected from the group of substances consisting of bethoxazin [CCN]+TX,copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX,cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal(295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX,quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX,triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide(IUPAC name) (347)+TX, an anthelmintic selected from the group ofsubstances consisting of abamectin (1)+TX, crufomate (1011)+TX,doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectinbenzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin(alternative name) [CCN]+TX, milbemycin oxime (alternative name)[CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX,selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate(1435)+TX, an avicide selected from the group of substances consistingof chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX, abiological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthurin-giensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX, a soil sterilant selected from the group ofsubstances consisting of iodomethane (IUPAC name) (542) and methylbromide (537)+TX, a chemosterilant selected from the group of substancesconsisting of apholate [CCN]+TX, bisazir (alternative name) [CCN]+TX,busulfan (alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX, an insect pheromone selected from the group ofsubstances consisting of (E)-dec-5-en-1-yl acetate with(E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate(IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordid in (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX, an insect repellent selected from the group of substancesconsisting of 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl(933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPACname) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPACname) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX, an insecticide selected from thegroup of substances consisting of 1-dichloro-1-nitroethane(IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX, a molluscicide selected from the groupof substances consisting of bis(tributyltin) oxide (IUPAC name)(913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX,cloethocarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate(172)+TX, fentin (347)+TX, ferric phosphate (IUPAC name) (352)+TX,metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX,niclosamide-olamine (576)+TX, pentachlorophenol (623)+TX, sodiumpentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX,tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb(840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX, anematicide selected from the group of substances consisting of AKD-3088(compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodamine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet(216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX, a nitrification inhibitorselected from the group of substances consisting of potassiumethylxanthate [CCN] and nitrapyrin (580)+TX, a plant activator selectedfrom the group of substances consisting of acibenzolar (6)+TX,acibenzolar-S-methyl (6)+TX, probenazole (658) and Reynoutriasachalinensis extract (alternative name) (720)+TX, a rodenticideselected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX, a synergist selected from the group of substancesconsisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name)(934)+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name)(903)+TX, farnesol with nerolidol (alternative name) (324)+TX, MB-599(development code) (498)+TX, MGK 264 (development code) (296)+TX,piperonyl butoxide (649)+TX, piprotal (1343)+TX, propyl isomer(1358)+TX, S421 (development code) (724)+TX, sesamex (1393)+TX,sesasmolin (1394) and sulfoxide (1406)+TX, an animal repellent selectedfrom the group of substances consisting of anthraquinone (32)+TX,chloralose (127)+TX, copper naphthenate [CCN]+TX, copper oxychloride(171)+TX, diazinon (227)+TX, dicyclopentadiene (chemical name)(1069)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, methiocarb(530)+TX, pyridin-4-amine (IUPAC name) (23)+TX, thiram (804)+TX,trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX, avirucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX, awound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX, and biologically active compounds selected from the groupconsisting of azaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX,bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX,difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX,epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX,fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX,flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil[35554-44-0]+TX, imibenconazole [86598-92-7]+TX, ipconazole[125225-28-7]+TX, metconazole [125116-23-6]+TX, myclobutanil[88671-89-0]+TX, pefurazoate [101903-30-4]+TX, penconazole[66246-88-6]+TX, prothioconazole [178928-70-6]+TX, pyrifenox[88283-41-4]+TX, prochloraz [67747-09-5]+TX, propiconazole[60207-90-1]+TX, simeconazole [149508-90-7]+TX, tebucon-azole[107534-96-3]+TX, tetraconazole [112281-77-3]+TX, triadimefon[43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin[131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc.BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin[361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin[133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin[248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin[175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb[12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX,thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX,captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid[1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3 ]+TX,tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX,copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX,coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper[53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX,nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX,iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX, anilazine[101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimetho-morph [110488-70-5]+TX, SYP-L190 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX,probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen[124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX,tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX,isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(disclosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX and1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright © 1995-2004]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds according to any one ofembodiments 1 to 12 with active ingredients described above comprises acompound according to any one of embodiments 1 to 12 and an activeingredient as described above preferably in a mixing ratio of from 100:1to 1:6000, especially from 50:1 to 1:50, more especially in a ratio offrom 20:1 to 1:20, even more especially from 10:1 to 1:10, veryespecially from 5:1 and 1:5, special preference being given to a ratioof from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewisepreferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4,or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5,or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75,or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750,or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practiced on the human or animal body.

The mixtures comprising a compound of according to any one ofembodiments 1 to 12 and one or more active ingredients as describedabove can be applied, for example, in a single “ready-mix” form, in acombined spray mixture composed from separate formulations of the singleactive ingredient components, such as a “tank-mix”, and in a combineduse of the single active ingredients when applied in a sequentialmanner, i.e. one after the other with a reasonably short period, such asa few hours or days. The order of applying the compounds according toany one of embodiments 1 to 12 and the active ingredients as describedabove is not essential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also besuitable for the protection of plant propagation material, for exampleseeds, such as fruit, tubers or kernels, or nursery plants, againstpests of the abovementioned type. The propagation material can betreated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound according to any one of embodiments 1 to 12. Theterm “coated or treated with and/or containing” generally signifies thatthe active ingredient is for the most part on the surface of the seed atthe time of application, although a greater or lesser part of theingredient may penetrate into the seed material, depending on the methodof application. When the said seed product is (re)planted, it may absorbthe active ingredient. In an embodiment, the present invention makesavailable a plant propagation material adhered thereto with according toany one of embodiments 1 to 12. Further, it is hereby made available, acomposition comprising a plant propagation material treated with acompound according to any one of embodiments 1 to 12.

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundaccording to any one of embodiments 1 to 12 can be carried out by anyknown methods, such as spraying or by dusting the seeds before sowing orduring the sowing/planting of the seeds.

The pesticidal/insecticidal properties of the compounds according to anyone of embodiments 1 to 12 can be illustrated via the following tests:

Diabrotica balteata (Corn Root Worm):

Maize sprouts placed onto an agar layer in 24-well microtiter plateswere treated with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions by spraying. After drying, the plates were infested withL2 larvae (6 to 10 per well). The samples were assessed for mortality 4days after infestation. The following compounds resulted in at least 80%mortality at an application rate of 200 ppm: 1, 2, 3, 4, 10, 11, 12, 13,14 and 15.

Euschistus heros (Neotropical Brown Stink Bug): Feeding/Contact Activity

Soybean leaves on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaves were infested with N2 nymphs. The samples wereassessed for mortality 5 days after infestation. The following compoundsresulted in at least 80% mortality at an application rate of 200 ppm: 1,2, 3, 4, 5, 6, 7, 8, 9, 10 and 12.

Myzus persicae (Green Peach Aphid): Feeding/Contact Activity

Sunflower leaf discs were placed onto agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation. The following compounds resulted in at least80% mortality at an application rate of 200 ppm: 1, 2, 4, 5 and 8.

Plutella xylostella (Diamond Back Moth): Feeding/Contact Activity

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10′000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality 5 days afterinfestation. The following compounds resulted in at least 80% mortalityat an application rate of 200 ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14 and 15.

Spodoptera littoralis (Egyptian Cotton Leaf Worm): Feeding/ContactActivity

Cotton leaf discs were placed onto agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality 3 days afterinfestation. The following compounds resulted in at least 80% mortalityat an application rate of 200 ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15 and 16.

Tetranychus urticae (Two-Spotted Spider Mite): Feeding/Contact Activity

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation. The following compoundsresulted in at least 80% mortality at an application rate of 200 ppm: 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12.

Thrips tabaci (Onion Thrips): Feeding/Contact Activity

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions. After drying the leaf discs were infested with a thripspopulation of mixed ages. The samples were assessed for mortality 6 daysafter infestation. The following compounds resulted in at least 80%mortality at an application rate of 200 ppm: 1, 2, 3, 4, 10, 11, 12, 13,14, 15 and 16.

The compounds of the invention can be distinguished from known compoundsby virtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, δ ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Furthermore, besides of the insecticidal properties, the compoundsaccording to any one of embodiments 1 to 12 have surprisingly shown tohave improved degradation properties compared with prior art compounds.Additionally, the compounds according to any one of embodiments 1 to 12have surprisingly shown to be less toxic to the environment, e.g. tobees or aquatic organisms, compared with prior art compounds.

What is claimed is:
 1. A compound of formula (I),

wherein Y¹ and Y³ are independently selected from H, halogen, cyano,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylsulfanyl, C₁-C₆-haloalkylsulfanyl,C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl andC₁-C₆-haloalkylsulfonyl; Y⁵ is selected from -i-CF(CF₃)(CF₃) and-1-CF₃-cyclopropyl; A is CH or N; R¹ is selected from H, C₁-C₆-alkyl,C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₇ cycloalkyl, C₃-C₇cycloalkyl-C₁-C₃-alkyl, —C(═O)H, C₁-C₆-alkylcarbonyl,C₃-C₇-cycloalkylcarbonyl, C₁-C₆-alkoxycarbonyl, aryl(C₀-C₃)-alkyl andheteroaryl(C₀-C₃)-alkyl, wherein each of C₁-C₆-alkyl, C₃-C₆ alkenyl,C₃-C₆ alkynyl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkyl-C₁-C₃-alkyl,C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxycarbonyl, aryl(C₀-C₃)-alkyl andheteroaryl(C₀-C₃)-alkyl is unsubstituted or substituted with 1 to 5substituents independently selected from halogen, cyano, C₁-C₆-alkoxyand C₁-C₆-alkoxycarbonyl; R² is selected from halogen, cyano,C₁-C₆-alkyl and C₁-C₆-haloalkyl; Q is H or cyano; or an agrochemicallyacceptable salt or N-oxide thereof.
 2. The compound according to claim 1wherein R² is selected from halogen and cyano.
 3. The compound accordingto claim 1 wherein R² is selected from chloro and cyano.
 4. The compoundaccording to any one of claim 1 wherein R² is cyano.
 5. The compoundaccording to claim 1 wherein Q is cyano.
 6. The compound according toclaim 1 wherein R¹ is selected from H, methyl, ethyl, —CH₂CH═CH₂,isobutyl, isopropyl, 2,2,2-trifluoroethyl, cyclopropylmethyl, —C(═O)CH₃,—C(═O)CH₂CH₃, —C(═O)cyclopropyl, —C(═O)OCH₃, —C(═O)OCH₂CH₃,—C(═O)CH(CH₃)(CH₃), —CH₂C≡CH, —CH₂CN, —CH₂—O—CH₃, —CH₂—O—CH₂—CH₃ and—CH₂-cyclopropyl.
 7. The compound according to claim 1 wherein R¹ isselected from from H, isobutyl, 2,2,2-trifluoroethyl, cyclopropylmethyl,—C(═O)CH₃, —C(═O)OCH₃, —C(═O)OCH₂CH₃, —C(═O)CH(CH₃)(CH₃), —CH₂—C—CH,—CH₂CN and —CH₂—O—CH₃.
 8. The compound according to claim 1 wherein Y¹and Y³ are independently selected from chloro, bromo, —CF₃, —CHF₂,—OCF₃, —OCHF₂, methyl, ethyl, —SCH₃, —SOCH₃, —S(O)₂CH₃ and CN.
 9. Thecompound according to claim 1 wherein Y¹ and Y³ are independentlyselected from chloro, bromo, —CF₃, —OCHF₂ and methyl.
 10. The compoundaccording to claim 1 selected from2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide;2-chloro-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide;2-cyano-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide;2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide;2-cyano-N-cyclopropyl-5-[1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide;2-chloro-5-[1-[2-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]-N-(1-cyanocyclopropyl)thiophene-3-carboxamide;5-[1-[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]-2-chloro-N-(1-cyanocyclopropyl)thiophene-3-carboxamide;5-[1-[2-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]-2-cyano-N-cyclopropyl-thiophene-3-carboxamide;5-[1-[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]-2-chloro-N-cyclopropyl-thiophene-3-carboxamide;2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide;2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]-N-ethyl-thiophene-3-carboxamide;2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]-N-methyl-thiophene-3-carboxamide;2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide;2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]-N-ethyl-thiophene-3-carboxamide;2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]-N-methyl-thiophene-3-carboxamide;2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide;and2-chloro-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide.11. A pesticidal composition, which comprises at least one compoundaccording to claim 1, or an agrochemically acceptable salt or N-oxidethereof, as active ingredient and at least one auxiliary.
 12. Thecomposition according to claim 11, which further comprises one or moreother insecticidally, acaricidally, nematicidally and/or fungicidallyactive agents.
 13. A method for controlling pests, which comprisesapplying a composition according to claim 11 to the pests or theirenvironment with the exception of a method for treatment of the human oranimal body by surgery or therapy and diagnostic methods practiced onthe human or animal body.
 14. A method for the protection of plantpropagation material from the attack by pests, which comprises treatingthe propagation material or the site, where the propagation material isplanted, with a composition according to claim
 11. 15. A coated plantpropagation material, wherein the coating of the plant propagationmaterial comprises a compound as defined in claim 1.